BIOMIMETIC ALKALOID SYNTHESES .15. ENANTIOSELECTIVE SYNTHESES WITH EPICHLOROHYDRIN - TOTAL SYNTHESES OF (+)-VINDOLINE, (-)-VINDOLINE, AND (+/-)-VINDOLINE AND A SYNTHESIS OF (-)-VINDOROSINE
BIOMIMETIC ALKALOID SYNTHESES .15. ENANTIOSELECTIVE SYNTHESES WITH EPICHLOROHYDRIN - TOTAL SYNTHESES OF (+)-VINDOLINE, (-)-VINDOLINE, AND (+/-)-VINDOLINE AND A SYNTHESIS OF (-)-VINDOROSINE
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DOI：
10.1021/jo00379a006
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发表时间：
1987-02-06
影响因子：
3.6
通讯作者：
BORNMANN, WG
中科院分区：
文献类型：
--
作者：
KUEHNE, ME;PODHOREZ, DE;BORNMANN, WG
描述了外消旋和各种对映体形式的长春花碱(1)和(-)-长春花碱(2)的全合成。它们是通过14-羟基己二胺中间体6和7的生成和非对映选择性环化而实现的。随后还研究了3-氧代他贝松碱(24)、3-氧代香草胺(26)和14-β-羟基乙烯基甲酰胺(15)对E环的氧化精制。Na-甲基他伯松(22)被氧化成环-D-收缩的α-酮内酰胺，23。
Total syntheses of vindoline (1) in racemic as well as in each enantiomeric form and of (-)-vindorosine (2) are described. They were achieved by generation and diastereoselective cyclizations of 14-hydroxysecodine intermediates 6 and 7. The subsequent oxidative elaboration of ring E was also studied with 3-oxotabersonine (24), 3-oxovincadifformine (26), and 14.beta.-hydroxyvincadifformine (15). Na-Methyltabersonine (22) was oxidized to a ring-D-contracted .alpha.-keto lactam, 23.